Polymerization process



Aug. 15, 1944. J. A- REID 2,355,925

' POLYMERIZATION PROCESS Filed July 14, 1941 JAMES A. REID mi y .s

a ATT R Y LKALI METAL lar Weight.

production from lowerboiling olens of lubriy cating oils land of lubricating oil stocks within `fins.

Patented Aug. 15, 1944 i Phillips Petroleum Delaware Company,` a corporation of Application July 14, 1941seria1No. 402,415

1s Claims.` (Croco-#$3.15)

This invention relates to the catalytic kconversion of olens to hydrocarbons of higher molecu- More particularly it relates tothe desired viscosity ranges and of superior characteristics in the presence of anactivemetal halide `and an alkali metal.. `More specifically, it relates to the polymerization of tertiary-base oleflns to',

form lubricating oilstocks. i

Ihe catalytic polymerization of unsaturated L aliphatic hydrocarbons, such as oleflns -or mixtures of them, to form compounds of` higher molecular lweight is well known. By using se-4 cohols, dehydrogenation` of the corresponding Y parafiins, depolymerization of more viscous poly- Amay, be prepared by thermal treatment of parafiln hydrocarbons, as well as by catalytic dehydrogenation.` Higher molecular lweight oleilns may be prepared either by'thermal `treatment of paraiins, resulting inthe production of oleins most of which possess shorter carbon chains thanthe original parailin,` or-byxcatalytic dehydrogenation `of higher hydrocarbons with the formation acteristics from gasoline vthrough the more vis-x cous oils to resinous and rubber-like materials.

In orderito convert oleflns to. polymers inthe` viscosity range of lubricating oils, active metal bandes, ksuch 'as aluminum chloride,` aluminum bromide/ferrie chloride or` bromide, zinc chloride, boron fluoride, zirconium chloride, and the like, are preferred catalysts, and are often called Friedel-Crafts type` catalysts; Various iodides may'alsobe used. 'Ihe Friedel-Crafts type catalysts may-be employed either alone or .in conjunction with various organic or inorganic modifiers, promoters, solvents, and thelike. In the production of polymers in the lubricant range, which may have molecular weights of Vabout 250 to 1000, although higher'or'- lower molecular i creasing with increase in reaction temperature.

'I'he materials-that may be used as polymerization charge stocks include ythe lower molecular weight normally gaseous or liquid aliphatic ole- In some cases other compounds, including diolefins such as butadiene, cyclopentadiene and 1 the like, acetylene-type` compounds, aromatic hydrocarbons, and even oxygem,y sulfur-,or nitrogen-containixig compounds may be converted with cleiins in the polymerization reactions, Since the characteristics ofthe polymerization product are dependent` in part upon the charge stocks, the composition ofthe oleiln mixture charged to` any particular polymerization system is accordingly controlled through adequate means solas to permit the production of desirable` polymers. In many instances it isdesirable to use ascharge only a single olefln` species, strictly purified to eliminate. other possible reactant materials. A

The olens may be obtained in a relatively pure state by dehydration of the appropriate a1- of oleilnshaving predominantly` the same num-` ber of carbon atoms in the molecule as theoriginal paraiiins.` Selected fractions `of oleiin-containing reflnerylproducts, such as the products from cracking stills, may also beused as charge stocks, especially afterchemical treatment for the removal of objectionable components from the mixtures. Since the polymerization reaction `is stronglyexothermic it may be' desirable to dilute the olefin with unreactive hydrocarbons in order to control the temperature and reaction rate more readily.H Dilution may also -be desirable to facilitate handling of the products. l

Although it has previously `been proposed to polymerize oleflns in the presence of an active metal `halide catalyst,` together with a Vsmall amountof hydrogen `halide, y,whereby inr general a more rapid polymerizationis obtained, in many cases the polymers so obtained, especially in the viscosityrange of lubricating oils, are quite nferior in one or more importantphysical characteristics to polymers prepared from the same charge stock using the same metal halide catalyst under the same conditions but in the substantial absence of any hydrogen halide. This is particularlytrue when the olens polymerized aretertiary-basey olens, or when tertiary-base yoleflns comprise an appreciable portion of an olenic hydrocarbonv material `which is being polymerized.` `In particular it `has been observed thatthe yviscosity index ofpolymers in the viscosity range of lubricating oils produced by the polymerization of tertiary-baseolens or olefin mixtures `containing tertiary-base olefins varies considerably with the amount of hydrogen halide present inthe mixture during the polymerization. In view of vthe importance of such physical.

properties, these variations are important and generally theyare of an undesirable natikire when formed in the presence of a hydrogen halide.V

By teritary-base oleins I intend to include, in general, such oleflnswhich correspond to the formula R2C=CRJ= `where each R is any alkyl group and each R is hydrogen or any alkyl group; Such oleiins, uponhydrolysis in an acidic medium, will generally yield a tertiary alcohol.

Typicallow-boiling tertiary-base olens are 2- methyl-propene, Z-methyl-l-butene, 2-methyl- Z-butene, 2-methyl-l-penten'e, 2.methyl-2pen tene, B-methyl-Z-pentene, and the like.v

In the absence of other contaminants I have found that the variation in quality of the polymeric oil produced by the conversion of an olefin in the presence of an active metal halide results primarily from the presence of a hydrogen halide in the system. Greater proportions of one or more hydrogen halides in such catalytic systems result in the production of low viscosity index products, other conditions remaining substantially the same. In such systems I have found that consistently uniform products of relatively high viscosity index are produced from tertiary- V base4 olefins, or from mixtures containing tertiary-base olens, onlyin the substantial absenc'e, of a hydrogen halide.

lHydrogen halides in the system may result from the addition of certain modie'rs, either as a direct reaction product or as a product of re- ;actionwith metal halide catalyst,y from there- .actioniwith the catalyst of some oxygen or sulfur compounds,'or the like, present in the charge A `suchas'water, mercaptans, alcohols, or 'the like, or. from-v decomposition interaction of metal .,halidecatalysts. of the Friedel-Crafts type with a hydrocarbon in the system. Thus although the selection of a-suitable catalyst and purification .of materials charged to the `system reduces the ',variation in` product quality, the variations can -not under most circumstances. be eliminated by {such'meana .I have now discovered that products of consistently desirable quality and uniformity can be produced through the use of a material in the polymerization zone which will remove any hydrogen halides from said zone.

An object of this invention is to produce improved lubricatingoil stocks.

:Another objectof this invention is to convert olefins into desirable lubricating oils.

Another object of this invention is to polymerizeftertiary-base olefins or olen mixtures vcontaining tertiary-base oleflns vto producehydrocarbons in theviscosity rrange of lubricating K oils having high viscosity index values.

, Asfurther objectof this invention is to provide a superiorcatalytic system for the conversion of polymerizable olens to polymers in the' viscosity range of lubricating oils.

, Still .another object of this invention is to polymerize tertiary-base volelns to products of desirable quality gand uniformity using a metal halide catalystl inY a system substantially free from hydrogen halide.'v

Further objects and advantages of this inventionwillbecome apparent from the accompanying disclosure and discussion.

My invention comprises, more specically, the use of an alkali metal in conjunction with, or associatedwith, an active metal halide of the Friedel-Crafts type, which does not react with thel alkali metalunder the conditions of use, for the reaction of `tertiary-base olens, or olen mixtures containing tertiary-base olens, at suitable temperature which will generally be found in the'range of about 0 to 200 F., and a pressure in the range of atmospheric to 500 pounds per square inch gauge or adequate to maintain a substantial proportion of the reactants in liquid phase, to produce products in the lubricating oil viscosity range'which possess higher viscosity index values, for example, than those produced in conventional catalytic systems. The reaction time, which depends greatly yon the catalyst, the temperature, the reactants, the extent of conversion, etc., is usually in the range of l/2 to 10 hours, although longer or shorterV times may be employed in specific cases. For example, a reaction time in the lower part of the range is desirable for polymerization when the activity of the catalyst is high, when the temperature of the conversion isin the upper part of the temperature range, when the reactants are relatively easily polymerizable, and/or the extent of conversion is maintained at a low value. An alkali metal does not catalyze the polymerization of an appreciable quantity of olefin under the conditions of reaction herein disclosed nor does it affect the activity of the active metal halide catalyst toany appreciable extent.

As is more completely brought out elsewhere ,in this disclosure, it is believed that the primary function of the alkali metal which is' associated with the active metal halide, or of other material which may be associated with the active metal halide in accordance with thisv disclosure, is to react with and remove from the polymerization zone hydrogen halide which may be present or formed. Whether or not this is the only function, or even the true function, is not conclusively hydrocarbons, such as oleflns, in the presence of a catalyst comprising an active metal halide, or a metal halide catalyst of the Friedel-Crafts type, associated with an alkali metal or, more broadly, associated with a material which inhibits the formation or continued existence of a hydrogen halide, and such use of the term catalyst in this specification and lin the accompanying claims is made with this in mind. The catalyst oi this invention can, in general, be appliedto any hydrocarbon reaction ordinarily catalyzed by a Friedel-Crafts type metal halide.' Thus it may be used in alkylation of saturated-type hydrocarbons with voleiins, and in the simple polymerization of olens. In manysuch reactions, however, the presence of a hydrogen halide is not deleterious, or markedly so, and some such reactions proceed only with extreme slowness in the virtual absence of a hydrogen halide from one source or another. For such reactions my catalyst will generally-not be applied. However, as brought out in the present disclosure the' use of my catalyst results in substantial improvements in the polymerization of tertiary-base olens to form lubricating oil stocks, and this feature will be more particularly discussed in this disclosure.

It has been reported in the literature that under rigorously attained, anhydrous conditions there is no reaction between an alkali metal such as sodium and a hydrogen halide such as hydrogen chloride. In the use of my catalyst, comprising a Friedel-Crafts type metal halide and an alkali metal, or the like, for the polymerization of tertiary-base olefins to form lubricating oil stocks, products of higherv quality result with well ,purified charge stocks, such purification including dehydration. However, it appears that the usual purification methods, even when a high purity is desired or obtained, are such that the beneficial actions of the alkali metal are not drogen halide.

` hereby appreciably inhibited or Vrendered-ineffective f l f Y. A n `alkali metal, especially; sodium or potas- '.fsium, whenadded to a hydrocarbon mixture conltainingfhydrogenhalide removes such hydrogen Vhalide very rapidly andcompletely, or as the case may be, takes it up `as rapidlyas it may be formed. Through adequate contact between alkali metal and thehydrocarbonphase, hydrogen hal-ide in the system may` thus bemaintainedat -f a very low value., To obtain intimate contact between the alkali metal and the other components `in the 4system it 'ispreferred that the metal be either` `very .finely divided `or in the liquid state. iInmost applications, the liquid alkali metal, such as sodium-potassium valloy or asolution of an valkali metal in another liquid metal such as mercury, is preferred to the finely divided solid to vprevent coating of the `liquid surface `by alkali -metal ghalide. Y

`iet `relatively low temperatures,v the alkali metr`als may be used vsatisfactorily in catalytic sys- {tems with any of the suitable metal halideicatalysts. kAs the temperature is increased, however,

some of those metal halides which may exist in a lower valence state may undergo reaction with `the sodium or other alkali metal, thus bringing about a deactivationy of the catalyst. For exam- .ple, -antimony pentachloride maybe used satisfactorily with sodium only at very low reaction` temperatures, since reduction` to antimony tri- Achloride occurs very readily. Thus, the more stable or less easily reduced met-al halides, such Liatswaluminum chloride, boronfluoride, zirconium qchloride and the like, may be` usedover a lmuch ywider range `of operating. conditions than the more readily reducedactive metal halide catalysts such -as antimony -pentachloride`, titanium tetra- `chloride and similar catalysts. i temperatures, `usually in excess'of250" F., slow At relatively'high reactionof the alkali metal, especially sodium, with the olen may occur; thus `anotherlimitation on the maximum conditions of reaction tem- `iperature and time in the system is imposed.

In these olefin polymerization systems, the active metalhalide catalyst is'normally used in a concentration of 0.5 to per cent, depending uponthereactivity of the charge, the catalyst .activity, the temperature level, the degree of agitation, etc. The proportion of alkalimetal used is determined by the rate of evolution of hydrogen halide in the reaction system, and by the effectiveness ofthe contact between the alkali metal and the conversion system. In most batch polymerizations, it has been lfound desirable to use from `25 to 100 per cent by weight as' much alkali metal as :active metal halide catalyst. A great proportion of the 4alkali metal is recovered unchanged from the system,however, so that a Arelatively small Y proportion of alkali metal is Anormally consumed `through reaction with hy- The large excess ofsodium or` other alkali metal is desirable to facilitate vremoval ofthe hydrogen halide from the system. In a continuous polymerization system,

lit is desirable to use a relatively high proportion tion conditions 4but which do vnot deactivate the active metal halide catalysts# Sometimes highly adsorptive materials, such as activated charcoal,

kaline earth metals, and othercompoundswhich react with hydrogen halide under the polymerizasilica gel,`alumina, or the like may alsobe used.

when'their nature and extent ofus'e is Vsuch as to include the function of `removal ot'hydro'gen halide. However, the alkali metals are the most satisfactory from the viewpointof the quality' of the hydrocarbon products.

-The polymerization is preferably conducted at a. suilciently high pressurefthat `atthe operating temperature a substantial concentrationo'f-ithe reactive olefin is maintained in theliquid reactnt mixture. Through adequateagitationlsatisfactory contact `of the reactants is established and control o the reaction-temperature through removal of the `exothermic heat of reaction is facilitated.

Ithas been previously found that straigltch'ain Vl-olens. are polymerizedat a very low rate by some yactive Ametal halide catalysts in the` absence of hydrogen halide, whereas the polymerization `is greatly augmented by the presence ofhydrogen halide in the polymerization systemwitloutudeleterious eiect .on the qualitycf` the product. 'I'hrough a combination of those observatix'isfwlth the teachingsof this invention, Iseveral-a'dvatageous polymerization processes: may beffoll'owed in applying the invention. `For example, theis'ooleflns in a -mixture of lso- `and normalfolens may be selectively polymerized yin acatalyticsystem containing a suitable active'lrnetalvhalideand alkali m'etal catalyst under such conditions that the iso-olefins are converted in V"substantial p roportion to polymers Vin the viscosity4v rangeof'lubricating oils which possess as high"viscosityindexes ascan be prepared from those reactants /using active metal halide catalysts. The less reoils and/ or with suitable additives to enhance such ol` both active metal halide catalyst and alkali metal to facilitate the reactiomsince the excess catalyst may be Vretained in the system for prolonged use. l

Besides the alkali metals, other materials may at times be employed in the polymerization `to vmaintain the hydrogen halide concentration at a very low value.4 Such materials include theV alkaline earth metals, oxides of the alkali and alactive oleflns which remain as `unrea'ctedcharge may be separated from the polymer and converted in a catalyst system employing an activemetal halide with a modifier such as hydrogen-chloride, as in the application Serial No. 397,472, filed June l0, 1941, of which Iam a coinventor. In such a .combination of processes, products of higher 'viscosity index are produced than can :be secured from a single conversion operation, and segregation of product types is achieved. For example, the polymer from the less reactive olens normally possesses a higher thermal stability 'than the polymer from the iso-olens.

The olefin polymers produced in the catalytic system herein disclosed may be used `in the production of organic chemicals, resins, plastics, etc.,

`in addition to possible use in the preparation of lubricating oils. For use in lubricatingoil preparation,- it is usually desirable to stabilize the olefin polymer toward-oxidation through 'non-destructive hydrogenation or through alkylationtolproduce a saturated product. lItmay further be desirable to compound vthesynthetic oil with natural properties as oxidation resistance, dispersingaction, and the like.

My invention will nowlbe illustrated inl 'conneciilm strength,

`tion with the accompanying drawing-Which shows diagrammatically one arrangement of apparatus by means of which my invention may be practiced in connection with the polymerization of olens.

A hydrocarbon charge stockcontaining poly- `merizable olefins is introduced' to' the system through conduit l0 controlled by valve IIl and is passed to reactor I2 wherein olefins are"co`n` verted to polymeric material. If this charge stock ,solid suspended in an inert hydrocarbon.

contains only a small amount of unreactive material 'it may at ltimes be desirable to add unre- Such diluentsk aid in the control of the subsequent polymerization and facilitate the handling of the resulting polymer. Catalyst for the polymerization reaction, such as an active metal halide, is `charged' to reactor I2 through conduit I5 conrtrolled; .byvalve I B. The catalyst is preferably Y mixed with an inert diluent, such as a paraffin .-hydrocarbon, before passing it to the reaction Zone 'I'his'facilitateshandling of the catalyst as well as providing an additional means for addingdiluent material to the zone. Alkali metal is introduced to reactor I2 through conduit VI con- .vtrolled by rvalve I8, or may be introduced with the metal halide through conduit I5. The alkali g metal may be introduced to the reactor in any convenient form, and even though it may be in the liquidtateat thetemperature of the reactor, it may be desirable to introduce it as a nely divided The n.polymerization is conducted under conditions suitable` to produce polymerssuitable for use as lubricating oil stocks-as discussed herein. 'Ihe reactor i2-may, if necessary, constitute more than onenchamber forcarryingout'the reaction `togetherwithappropriate: heaters, coolers, stirrers -the like.known.,to' the art, and may be operatedbatchwise orcontinuously. Polymerization ei'iiuent can .then be passed through conduit 22 controlledbyvalve 23 to separator 24 in which anycatalytic material, valkali metal and other non-,hydrocarbon material may be separated from polymericv` hydrocarbon material. able, polymerization eilluent can be removed from 4the `system from reactor I2 through conduit 20 ACmtrolled-by .valve 2i. However, it is generally preferable. to passr the reaction mixture to separator 24.` Separation of solid material in separator 24, bothcatalytic and non-catalytic, may be accomplished by settling, filtering, centrifuging or some other suitable means.v When the actlvity'of the catalyst is stillv high, having been butslightly decreased by the previous polymerization reaction, Vit may be recycled-to the reactor I2 through conduit 25 controlled by valve 26 together with any alkali metal contained therewith, When, however, it is desirable to remove spent catalyst from the system for.subsequentregeneration. or other treatment` thismay be done by meansof conduit l21 controlled by valve 28. When such a procedure is lfollowed, alkali metal is separated from spent catalyst in means notA shown and then returned to the reactor I2 for removal of additional quantities of hydrogen halide.

Since .all traces of catalyst and alkali metal -are not usually removed by 'mechanical separation, vit is desirable to pass the polymerization When desirwhich is polymeric in nature but not of high enough molecular weight nor of suitable viscosity to be included in a lubricating oil stock is re- `movedfrom the fractionator through conduit 42 controlled by valve 43 and then through'puriiier 44 to remove any undesirable products such as compounds containing oxygen or halogen that have lbeen formed or'segregated in the 'fractionator. Such polymeric material substantially free from undesirable compounds is passed through conduit 4l controlled `by valve 4S 'back to the reactorv I2 therein lto be subjected to vfurther polymerizatiom Any desired portion or all of such material may be removed from the `terial lighter than that passed-through conduit 42 and containing a substantial portion of unreacted charge stock and diluent material passes through conduit 41- controlled by valve 43 to an auxiliary fractionator 50. In fractionator 94 the charge may be separated into alight and a heavy fraction which may be removed from the process through conduits 53 and/or II, respectively, controlled by valves 34 and 52, respectively. When it ls desirable, however, to retain at leasta part of this material in the process eitherone or both fractions may be admixed with the stream in conduit 42 through conduit 60 controlled by valve II by proper manipulation of valves 56 and Il in conduits l! and I1, respectively, and valves 54 and 52- in conduits 53 and 5I, respectively. When a portion of the material passing through conduit 41 may be re'- cycled directly to the reactor, this may be accomplished by reintroducing to the reactor material removed through conduit 49 controlled by valve 59. The non-volatilized material in Iractionator contains polymers in the viscosity range yoi' lubricating oils, and may be recovered through conduit and conduit 69 controlled by valve 69, but generally this material is passed through conduit 40 controlled by valve 4Ito vacuum fractionator 62. In the vacuum fractionator the polymers are separated into a series oi.' fractions of different viscosities and removed from said fractionator through one or more conduits 19, 1|, 12, and 13 controlled by valves 14, 15, 1I

vand 11, respectively. Each of these fractions are subjected to subsequent treatment. such vas .and 88, respectively, and valves |92 and |93 in conduit 9'4. Hydrogenated polymer fractions in the viscosity range of lubricating oil are removed from the hydrogenators through conduits eiiluent, still-containing residual solid material,

through conduit 30 controlled 'by valve 3I4 to absorber 32 lin which al1 traces of 'catalytic and other solid material are removed;r This may be system. Material charged tothe iractionator 'lo 94,95, 96, and 91 controlled by valves Il, 99, |00, and IIII, respectively and passed to equipment not shown where they may be stored, or blended and compoundedto` make iinished oils. The hydrogenation reaction is readily accomplished at temperatures of about 3D0-550 F. and 200 to 3000 pounds per square inch hydrogen pressure using `a catalyst such as reducednickel on kieselguhr. The residue from iractionator l2 is removed through conduit 33 controlled by valve 64 either to be rejected or for further processing not shown. When desired, however, at least a part or all of the fraction may be passed through conduit 39 controlled by valves 9B and i1 to the incoming charge stock in conduit I0. Similarly, a part oi. the polymeric materiai removed ,from Ai'ra ctionai:or 3l through conduit Il may be passed into conduit I! throuh vconduit; It! controlled by valve 31 for further Processingdn reactor i2 beiore being subjected to the hydrogenation step. Any oi the lower `trailing iractions `from fractionator l2 mayalso b9, recycled to the reactor. by means not shown. It lstobe appreciated that the drawing :lust described is diagrammatic only., The various pieces of equipment illustrated and discussed are conventional `in natureV andyin any application oi'hour inventionthere will be yassociated with the individual units shown various pumps, heaters,vcoolers, reilux accumulatore. heatexchangyers.-fractionating columns, temperature indicatlng andcontrol devices. and the like known in the art and whlchmaybe suitably supplied for any particular case byone skilled in the art following-theA teachingsof the reaction conditions and .material Allows disclosed and discussed herein. v l

'.My invention will Ibeffurther illustrated by iollowing'specinc exampleawhich show various advantages of the invention buty which are nog necessarilylto be construed as limiting the inventiijiml f t A; charge stockfcontaining l87.8 per cent isoi hutylene,'2.8 per cent propylene plus normal 'butene," and the krer'nainin'g per cent isobutene, was

polymerized .in a pressureauto'clave using zir- I c'onium tetrachloride fcatalyst. The temperature was 'kept at 1l53F.; fand thepressurev was the .vapor pressure of thehydrocarbon mixture. Adequate stirring` was providedrthe reaction was `substantially complete after ilve hours. No unusual eil'ort1was made to'keep the system i'ree `from hydrogen halide during. this polymerization period. :Approximately twenty per centof the polymer-productjwas in the viscosity range oi' lubricating oils. Properties of fractions in this The run ycltedin"'ljhrample*I was repeated `ex*- cept` that anumber of thin slices of clean sodium metal were placed inthe reactor. About 18 per cent of the polymer product was in the viscosity range ,of lubricating oils. Properties of fractions in this range are given in Table II.

vTable Il W vissen w Viscosity Fraction i at2l0 s.U.v find ser 9a 42.4 so sac 71 sas n The viscosity indetto!` the oil fractions obtained Afrom this run were consistentlyhigher than the ment in `viscosity index` has been obtained Table .UI v

. Viacosit Viscosity Fraction at 210 s. U. v. l d

9 35. 2 35 10 47. 6 24 1l. 56. 0 15 in 65. 7 18 This run demonstrated the lowering of the visder an inerthydrocarbon to a temperature of l about 210 F. Two parts of this alloy was placed in a glass reaction flask equipped with a motor driven stirrer and'contalnlng about `100` parts oi' parailln hydrocarbon. 'I'hissodium-potassium alloy was liquid at room temperature. One part aluminum chloride was added to the reaction ask. While stirring continuously,.the temperature of the ilaskwas increased to 220 F. The flask was held at this temperature and four additional parts of aluminum chloride was added. There was no evidence of reaction between the sodium-potassium alloy and the aluminum chloride. The ilask and its contents were allowed to cool to room temperature. The system was found to be highly active for the polymerization oi' various iso-oleiln mixtures. This run showed that aluminum chloride catalyst is not deactivated by sodium or potassium metal in this temperature range.

I claim:

1. In a process for the production of hydrocarbons in the viscosity range -of lubricating oils from low-boiling olefin hydrocarbons. the improvement which comprises subjecting a .charge stock consisting of hydrocarbon material containing such olefin hydrocarbons to reaction Vunder oleiln polymerization conditions in the presence of an active metal halide catalyst associated with an alkali metal, the latter being sufl ilcient to react with all hydrogen halide and viscosity indexes of similaroilfractions obtained from therun cited in Example 'I .f Thls improveother impurities which have an adverse influence on the character of the polymers formed and being essentially unreactive asan .oleilnpolymerizing catalyst under the reaction conditions.

2. A process for the productionv of hydrocarbons in the viscosityl range of lubricating` oils and having relatively `high viscosity indexes, which comprises polymerizing a tertiary-base olen in the presence of a Friedel-Crafts type catalyst associated with an alkali metal to form polymers in the lubricating oil range', said alkali metal being essentially unreactive as an olen polymerizing catalyst under said conditions and being suflicient t react with all hydrogen halide and other impurities which have an adverse iniiuence on the character of the polymers formed, and said Friedel-Crafts type catalyst being substantially unreactive with said alkali metal under the polymerizing conditions, and subsequently separating the hydrocarbons in the viscosity range of lubricating oils so produced.

3. A process according to claim 1 in which the alkali metal is sodium. f o 4. A process according to claim 2 in which the alkali metal is sodium.

v5. A process for producing hydrocarbon oils which comprises, polymerizing tertiary-base olefns at a polymerization temperature not greater than 200.F. in the presence of an active metal halide of the `Iriedel-Crafts type associated with an alkali metal to form polymers in the lubricating oil range, said alkali metal being essentially unreactive as an olefin polymerizing catalyst under said conditions and being suiiicient to re- .act with all hydrogen halide and other impurities ywhich have an adverse influence on the character of the polymers formed, kand the metal halide being nonreactive with the alkali metal under the conditions of polymerization.

6. A lprocess for polymerizing low-boiling, tertiary-base oleiins, which comprises polymerizing such an olen at a polymerization temperature not greater than 200 F. in the presence vof a catalyst comprising an active metal halide of the Friedel-Crafts type associated with an alkali metal to -form polymers in the lubricating oil range, said alkali metal being sufficient to refact-with'all hydrogen halideand other impurities "which have an adverse influence on the character of the polymers formed and being essentially unreactive .as an olen polymerizing catalyst under the reaction conditions.

7. A process for polymerizing a low-boiling, tertiary-base oleiin, which comprises polymerizing said oleiin at a polymerization temperature not greater than 200 F. in the presence of a catalyst comprising aluminum chloride associated with an alkali metal to form polymers in the lubricating oil range, said alkali metal being suiilcient to react with all hydrogen halide and other impurities which have an adverse iniiuence on the character of the polymers formed and being essentially unreactive as an olefin polymerizing catalyst under the reaction conditions.

8. A process for polymerizing a low-boiling, tertiary-base oleiin, which comprises polymerizing said 'olefin at a polymerization temperature not greater than 200 F. in the presence of a catalyst comprising zirconium tetrachloride associated with an alkali metal to form polymers in the lubricating oil range, said alkali metal being sufficient tov react with all hydrogen halide and i other impurities which have an adverse influence on the character of the polymers formed and being essentially unreactive as an olen polymerizing catalyst under the reaction conditions. 9. A process for polymerizing a low-boiling,

.tertiary-base olefin, which comprises polymerizing said olefin at a polymerization temperature not greater than 2003 F. in the presence of a catalyst comprising aluminum chloride associated'with sodium to form polymers in the lubricating oil range, said sodium being suilicient to react with all hydrogen halide and other impurities which have an adverse intiuence on the character of the polymers formed and being essentially unreactive as an olefin polymerizing `catalyst under the reaction conditions.

10. A process for polymerizing a low-boiling, tertiary-base olefin, which comprises polymerizing said oleiin ,at a polymerization temperature not greater than 200 F. in the prsence of la catalyst comprising zirconium tetrachloride associated with sodium to form polymers in the lubricating oil range, said sodium being sufficient to react with all hydrogen halide and other impurities which have an adverse influence on the character of the polymers formed and being essentially unreactivev as'an olefin polymerizing catalyst under the reaction conditions.

11. A process for polymerizing oleflns,j`which comprises polymerizing a low boiling tertiarybase olefin in liquid phase at a temperaturebetween 0 and 200 F. in the presence of ameta'l halide catalyst of the Friedel-Crafts type 'associated with an alkali metal, said alkali metal being in a liquidl state and suilicient vto react with all hydrogen halide and other impurities which have an adverse influence on the character of the polymers formed and being essentially unreactive as an olefin polymerizing catalyst under the reaction conditions. n

12. A process for polymerizing olens', which comprises polymerizing `a vlow-boiling tertiary- `:iase oleiin in liquid phase at a temperature between 0 and 200 F. in the presence of aluminum chloride associated with an alkalir metal, said alkali metal being in a liquid state-and suflicieht to react with all hydrogen halide and otherimpurities which have an adverse inuence onthe character of the polymers formed. and'being essentially unreactive as an olefin polymerizing catalyst under the reaction conditions.

13. A process for polymerizing oleiins, which comprises polymerizing a low-boiling tertiarybase olelin in liquid phase'at a polymerization temperature not greater than 200 F. in the presence of a metal halide catalyst ofthe Friedel- Crafts type associated with an alkali metal, said alkali metal being suiiicient to react with 'all hydrogen halide and other impurities which have an adverse influence on the character of the polymers formed and being essentially unreactive as an oleiin polymerizing catalyst under the reaction conditions.

14. A process for polymerizing oleiins, which comprises polymerizing a low-boiling tertiarybase olefin in liquid phase at a polymerization temperature not greater than 200 F. in the presence of aluminum chloride associated with an alkali metal, said alkali metal being sufficient to react with all hydrogen halide and other impurities which have an adverse influence on the character of the polymers formed and being essentially unreactive as an olefin polymerizing catalyst under the reaction conditions.

l5.`A process for polymerizing isobutylene, which comprises polymerizing isobutylene in liquid phase at a polymerization temperature not greater than 200 F. in-the presence of a metal halide catalyst of the Friedel-Crafts type associated with an alkali metal, said alkali metal being suiiicient to react with all hydrogen halide and other impurities which have an adverse influence on the character of the polymers formed and being essentially unreactive as an olen polymerizing catalyst under the reaction c0n-. ditions.

16. A process for polymerizing olefins,Y which comprises subjecting a charge stock consisting 0! hydrocarbon material comprising a low-boiling oleiin to polymerization conditions in liquid phase at a, polymerization temperature not 17. The process of claim 16, in whichsaid metal halide is aluminum chloride and said alkali metal is sodium.

18. The process of claim 16 in which said low- 5 boiling olefin is a tertiary-base olen. v

JAMES A. REID. 

